biofuels presentation.pptx
Post on 03-Dec-2015
259 Views
Preview:
TRANSCRIPT
TRENDS IN TECHNOLOGY FOR PRODUCTION OF BIOFUELS AND BIO-DERIVED CHEMICALS
Bio-fuels
Biodiesel and Bio-lubricants
Green Diesel
Alcohols for fuel additives
Jet Fuels
Biodiesel and Bio-lubricants
Biodiesel production increased over 1000% in the past decade
Biodiesel capacity Worldwide in 2012: 5,670 MMgpy
Biodiesel earns $1.50 per gallon under the U.S. RFS program
1st GENERATION BIODIESEL PLANTS
Transesterification
Homogeneous catalysts
Poor Glycerin Quality
High Feedstock Cost
Emissions issues
2nd GENERATION BIODIESEL PLANTS
Transesterification
Heterogeneous catalysts
Difficult Separation of Glycerin
Lower Feedstock cost
High Capital Investment
3rd GENERATION BIODIESEL PLANTS
Hydrolysis followed by Esterification using Catalytic Distillation
Heterogeneous catalysts
Easy separation of high quality Glycerin
Lowest Feedstock cost
Lower Capital Investment
OILFFA
CONTENTRELATIVE
PRICEPRICE(¢ / #)
PFAD (Palm Fatty Acid Distillate) 85-90% Low 27
Beef Tallow: choice prime 5-6% Medium 32
Beef Tallow: Special 10% Medium 30
Beef Tallow: No. 1,2,3 10-35% Low 31
Grease• White A,B• Yellow• House• Brown (trap)
8-10%15%20%50%
MediumMedium
LowLow
32282625
Poultry Fat 30
Algae Oil 4-15% Medium ?
Soybean Oil 2-3% High 39
Biodiesel and Bio-lubricants
FAT
SPLITTING COLUMN
500°F @ 850 PSIG
WATER
STEAM900#
FLASH VESSEL
FL
AS
H V
ES
SE
L
STEAMPV
LV
PV
TV
PV
TV
LV
PV
STEAM
LV
OIL WATER INTERFACE
PRODUCTION OF FATTY ACIDS
PRODUCTION OF BIODIESEL &
BIOLUBRICANTS
25% GLYCERIN
MU
LT
IPL
E E
FF
EC
T
PR
EC
ON
CE
NT
RA
TO
R
CATALYTIC DISTILLATION
COLUMN
350°F @ 200 PSIG
CRUDE FAME CIRCULATION PUMP
CAT. DIST. COLUMN REBOILER
WATER CIRCULATION
PUMP
METHANOL COLUMN REBOILER
METHANOL CIRCULATION
PUMP
FAT CIRCULATION
PUMP
FAME STRIPPING COLUMN REBOILER
FAT CIRCULATION
PUMP
METHANOL COLUMN OVERHEAD CONDENSER
FAME TO TANK FARM
WASTEWATER TO DISPOSAL
TO VACUUM J ETS
METHANOL DEHYDRATION COLUMN
METHANOL COLUMN OVERHEAD RECEIVER
FAME COLUMN OVERHEAD CONDENSER
FAME COLUMN OVERHEAD RECEIVER
FAME STRIPPING COLUMN
FV
FV
FV
LV
LV
LV
LV
METHANOL
Biodiesel and Bio-lubricants
Green Diesel
Considered a drop-in hydrocarbon replacement for Diesel
Earns $1.65 per gallon under the U.S. RFS program
Only a few operational plants currently
•HYDROTREATING – Hydrodeoxygenation•High
hydrogen consumption
•Complicated separations
•Low value side products
•DECARBOXYLATION – Hydro-decarboxylation•Less
hydrogen used
•Some complicated separations, purge loss
•Hydrogen recycle expensive
•HYDROTHERMAL DECARBOXYLATION•No
hydrogen needed
•Simplified separations
SPLITTING TO MAKEFATTY ACIDS
TRANS-ESTERIFICATION
HYDROGENATION15 mols H2/mol
triglycerideParrafinic Biodiesel
LOW TO MEDIUMFATTY ACID
CONTAINING OILS
MEDIUM TO HIGHFATTY ACID
CONTAINING OILS
BIODIESEL/BIOLUBRICANTS
Fatty Acid Methyl Ester Biodiesel
MILD HYDROCRACKING/
ISOMERIZATIONBiojet Fuel
NATURALTRIGLYCERIDES
CATALYTIC DISTILLATION
DECARBOXYLATION1 mol CO2 removed/
mol fatty acidParrafinic Biodiesel
BIODIESEL/BIOLUBRICANTSFatty Acid Methyl
Ester Biodiesel
GLYCEROL
GREEN DIESEL
Catalyst volume will change as a function of catalyst type and whether the catalyst is incorporated within structured catalytic packing or whether the catalyst is conventionally charged
Pilot Plant Reactor Type Volume of Catalyst
Design Pressure
Design Temp.
Liquid Feeds
Gas Feeds Feedstock Product
Transesterification Packed Bed 2,000 ml
100 bar
(1500 psig)
300°C
(575°F)
2 1 Triglycerides Biodiesel / Biolubricants
Green Diesel – Hydrodeoxidation (HDO)
Packed BedMolten Salt Bath Furnace
250 ml
70 bar
(1000 psig)
375°C
(700°F)
1 2 Triglycerides Diesel range parrafins
Catalytic Distillation
Heterogeneous Catalyst Loaded Column
2”x20 ft.
50 bar
(750 psig)
200°C
(400°F)
2 1 Fatty acids Biodiesel / Biolubricants
Catalytic Decarboxylation (CDC)
Packed Bed 5 zone electric
heater50 ml
30 bar
(450 psig)
350°C
(650°F)
1 2 Fatty acids Diesel range parrafins
Hydrothermal Decarboxylation
Packed Bed 5 zone electric
heater50 ml
180 bar
(2600 psig)
350°C
(650°F)
2 0 Triglycerides Green Diesel
Mild Hydrocracking/ Isomerization
Packed bed 5 zone electric
furnace50 ml
100 bar
(1500 psig)
375°C
(700°F)
1 2Biodiesel
range parrafins
Bio-SPK (biojet fuel)
Alcohols for fuel additives
Worldwide ethanol production in 2012: 28,000 MMgpy
10% blend wall reached in US. Projected gasoline consumption 133 billion gallons
Traditional ethanol earns $0.95 per gallon under the U.S. RFS program
1st GENERATION
Corn from ethanol
Food v. fuel debate
Cannot be put in pipeline
Low energy density
(70,000 Btu/gal – 19.6 MJ/L)
Corrosion issues
2nd GENERATION
Cellulosic ethanol
Solves debate
Earns higher credit
Same issues as traditional ethanol
3rd GENERATION
N-Butanol from waste starch or sweet sorghum
Solves debate
Can be put into pipeline
Energy density closer to gasoline
(110,000 Btu/gal – 29.2 MJ/L)
No Corrosion issues
Can be put into diesel as well.
Blend wall is increased to 12%
OPPORTUNITIES FOR N-BUTANOL
More toxic to the organisms. Lower yields make batch process un-economical
Most organisms make iso-butanol
n-butanol is used as a chemical intermediate for the production of a number of valuable chemicals such as: Butyl Acetate, Butyl Acrylate, Glycol Ethers, etc.
Expected to be a 9.4 billion per year market by 2018.
China currently consumes 35% of the n-butanol produced
CHALLENGES FOR N-BUTANOL
Alcohols for fuel additives
AQ
UEO
US
SEPA
RATO
R
FEED FROM FERMENTER
SO
LVEN
T CO
LUM
N
MIXED ALCOHOL
BUTANOL
WATER
100°C 117°C D
ECAN
TER
Solution: Immobolized organism with continuous removal of butanol
Jet Fuels
Current Jet fuel demand is 5 million barrels per day.
Now earns RIN credits of $1.50 - $1.65 per gallon under RFS
Fuel costs are approximately 35 – 45% of an airlines cost. Volatility is damaging.
•HYDROTREATING FOLLOWED BY HYDRO-ISOMERIZATION•Consumes
hydrogen•Second
reactor system
•Complicated separations
•Lowers density of fuel which limits the amount of bio-fuel that can be used (ASTM 7566: 50% max)
•DECARBOXYLATION AND ISOMERIZATION IN ONE STEP.•Less
hydrogen used
•Single reactor train
•Making rings and minimizing cracking increases density of fuel.
Modularity
The concept of modularity for the design of pilot plants, demonstration plants and small commercial plants was pioneered by our group. This concept now has found universal acceptance in terms of maintaining QA/QC controls, assembly procedures and reducing overall project costs .
Aspen Plus Simulation
+Heat & Material
Balances+
Process Flow Diagrams
Process & Instrumentation
Diagrams+
Equipment Specs+
Instrument Specs+
Control Philosophy
Detailed Engineering
+3D Plant Design
Procurement+
Construction+
Field Testing
Phase 1Phase 1 Phase 2Phase 2 Phase 3Phase 3 Phase 4Phase 4
Project Implementation Sequence
Catalyst Research Systems
• The basic requirement in the analysis of catalytic reactors is a rate expression for the reaction concern.
• The choice of a suitable reactor for carrying out experiments under conditions where meaningful kinetic rate expressions can be obtained is of very great importance.
Unitel: Breadth of Application
Catalyst Research
Petro-chemicals
Energy Research
Misc. Unit Operations
Pharmaceutical &
Nutraceutical
PE
Gasification
Petroleum Refining
Polymerization
Environmental
Transesterification
H C O C R1 + CH3 CH2
H O O H
H
MIXED TRIGLYCERIDE +ETHANOL
O C
O
R1
Catalyst
+
ETHYL ESTERS +
H C O H
H C O H
H
H C O H
H
GLYCERINE
H C O C R 2 + CH3 CH2
O O H
H C O C R3 + CH3 CH2
O O H
CH3 CH2
O C
O
R2
CH3 CH2
O C
O
R3
CH3 CH2
=
Green Diesel – HydroDeOxidation(HDO) Pilot Plant
“Green Diesels” consist of diesel-range (C12-C18) paraffins of high cetane numbers
Deoxygenation by hydrogenation of triglycerides
No glycerin byproduct
NiMo catalysts
Hydrotreat/hydrocrack the trigylcerides – remove O (Oxygen) atoms as H2O
Very high hydrogen consumption
Yield = 50-60%
Big H2 plant investment; or incorporated into a refinery
C57H104O6 + 15H2 6H2O + C3H8 + 3 C18H38
triglyceride hydrogen water propane diesel
CO2 + H2 CO + H2O CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O
The Chemistry – Biodiesels
Catalytic Distillation
Fatty Acids
R1 — C — OH + OH — CH2 — H
O
O
O
Methanol Water Methyl Ester
R1 — C — O — CH2 — H + H2O
O
O
O
R2 — C — O — CH2 — H + H2O
R3 — C — O — CH2 — H + H2O
R2 — C — OH + OH — CH2 — H
R3 — C — OH + OH — CH2 — H
Catalytic DeCarboxylation(CDC) Pilot Plant
Decarboxylation – the critical step towards jet fuel
decarboxylationthe critical step towards jet fuel
R1 — C — OH
O Heterogeneous Catalyst
Fatty Acids
R1H + CO2
ParaffinicHydrocarbon
Carbon Dioxide
∆G (300 C) = -83.5 KJ /mol∆H (300 C) = 9.2 KJ /mol
Heterogeneous Catalyst
R1H
ParaffinicHydrocarbon
n-C17H34
C10-C15
BranchedParaffins
Mild Hydrocracking&
Hydroisomerization
Decarboxylation
Catalytic DeCarboxylation(CDC) Pilot Plant
FATTY ACID FEED
HV-xxx
P-XXXDIAPHRAGM METERING FEED PUMP
HV-xxx
F-xxx
VENT
xxx bar
PCVxxx
PIxxx
PIxxx
Set at xxx bar
PSVxxx
HV-xxx
DRAIN
WAH
WAL
V-xxxFATTY ACID FEED TANK
HV-xxx
WTxxx
WIxxx
E
TIC
xxx
TExxx
HTRxxx
TYxxx
HSxxx
Mxxx
HS
xxx
E
E
PTxxx
PI
xxx
PIxxx
HV-xxx
DRAIN
E
CK-xxxHV-xxx
VENT
PSVxxx
PIxxx
PIxxx
CK-xxx
NITROGEN(>10 BAR)
FC
FVxxx
FTxxx
FIC
xxx
MASS THERMAL
F-xxx
IA
S
VENT
XYxxx
XVxxx
HS
xxx
FC
CK-xxx
CARBON DIOXIDE (>30 BAR)
CK-xxxFC
FVxxx
FTxxx
FIC
xxx
MASS THERMAL
F-xxx
PCVxxx
IA
S
VENT
XYxxx
XVxxx
HS
xxx
FC
PTxxx
PI
xxxPIxxx
VENT
PSVxxx
F-xxx
HYDROGEN(>30 BAR)
PTxxx
PI
xxxPIxxx
PCVxxx
PCVxxx
CK-xxx
Catalyst charge: 50 mLReactor internal volume: 100 mLMaximum system pressure: 30 bar (~450 psig)Maximum system temperature: 350°C (~650°F)Number of liquid feeds: 1Maximum LHSV of liquid feed: 2Number of gas feeds: 3
2 high pressure, 1 low pressure
FRN-xxxSPLIT TUBE MULTI ZONE FURNACE
RX-xxxTUBULAR REACTOR
TO VENT
VENT
PSVxxx
PTxxx
PI
xxx
PIxxx
F-xxx
PIxxx IA
I PPYxxx
PVxxx
FO
FCAS
S
VENT
KYxxxKV
xxx
HSxxx
TO GC / ANALYTICAL
FQTxxx
FQIxxx
FQI-xxx
F-xxx
LITxxx
PCVxxx
LICxxx
IA
I P
LYxxx
LVxxx
FC
ALKANE PRODUCT
WAH
WAL
V-xxxALKANE PRODUCT RECEIVER
HV-xxx
WTxxx
WIxxx
E
CATALYTIC DECARBOXYLATION PILOT PLANT
Drawing No.: ---
Project No.: xxx
Sheet No.:5/5
Drawn by:JAB
Rev No.: 0
Date:8/26/10
411 Business Center Drive, Suite 111Mt. Prospect, IL 60056 USAwww.uniteltech.com
CONFIDENTIAL
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
HV-xxx
HV-xxx
TI
xxx
TExxx
TI
xxx
TExxx
TI
xxx
TExxx
TI
xxx
TExxx
TI
xxx
TExxx
PTxxx
PI
xxxPIxxx
VENT
PSVxxx
FC
FVxxx
FTxxx
FIC
xxx
MASS THERMAL
F-xxx
PCVxxx
IA
S
VENT
XYxxx
XVxxx
HS
xxx
FC
PTxxx
PI
xxxPIxxx
VENT
PSVxxx
F-xxx
PTxxx
PI
xxxPIxxx
PCVxxx
Mild Hydrocracking – Isomerization Pilot Plant
Optimizing the jet fuel
Heterogeneous Catalyst
R1H Paraffinic
Hydrocarbonn-C17H34
C10-C15 Branched
ParaffinsMild
Hydrocracking & Hydroisomerizatio
n
Mild Hydrocracking – Isomerization Pilot Plant
MILD HYDROCRACKING – ISOMERIZATION PILOT PLANT
Drawing No.: ---
Project No.: xxx
Sheet No.:5/5
Drawn by:JAB
Rev No.: 0
Date:8/26/10
411 Business Center Drive, Suite 111Mt. Prospect, IL 60056 USAwww.uniteltech.com
CONFIDENTIAL
ALKANE FEED
HV-xxx
P-XXXDIAPHRAGM METERING FEED PUMP
HV-xxx
F-xxx
VENT
xxx bar
PCVxxx
PIxxx
PIxxx
Set at xxx bar
PSVxxx
HV-xxx
DRAIN
WAH
WAL
V-xxxFEED TANK
HV-xxx
WTxxx
WIxxx
E
TIC
xxx
TExxx
HTRxxx
TYxxx
HSxxx
Mxxx
HS
xxx
E
E
PTxxx
PI
xxx
PIxxx
HV-xxx
DRAIN
E
CK-xxxHV-xxx
VENT
PSVxxx
PIxxx
PIxxx
CK-xxx
NITROGEN(>10 BAR)
FC
FVxxx
FTxxx
FIC
xxx
MASS THERMAL
F-xxx
IA
S
VENT
XYxxx
XVxxx
HS
xxx
FC
VENT
PSVxxx
PIxxx
PIxxx
FC
FVxxx
FTxxx
FIC
xxx
MASS THERMAL
F-xxx CK-xxx
LOW PRESSURE H2/H2S ACTIVATION GAS(>10 BAR)
IA
S
VENT
XYxxx
XVxxx
HS
xxx
FC
CK-xxxFC
FVxxx
FTxxx
FIC
xxx
MASS THERMAL
F-xxx
PCVxxx
IA
S
VENT
XYxxx
XVxxx
HS
xxx
FC
PTxxx
PI
xxxPIxxx
VENT
PSVxxx
F-xxx
HIGH PRESSURE HYDROGEN (>100 BAR)
PTxxx
PI
xxxPIxxx
PCVxxx
PCVxxx
PCVxxx
CK-xxx
Catalyst charge: 50 mLReactor internal volume: 100 mLMaximum system pressure: 100 bar (~1500 psig)Maximum system temperature: 375°C (~700°F)Number of liquid feeds: 1Maximum LHSV of liquid feed: 2Number of gas feeds: 3
(1 high pressure, 2 low pressure)
FRN-xxxSPLIT TUBE MULTI ZONE FURNACE
RX-xxxTUBULAR REACTOR
TO VENT
VENT
PSVxxx
PTxxx
PI
xxx
PIxxx
F-xxx
PIxxx IA
IP
PYxxx
PVxxx
FO
FCAS
S
VENT
KYxxxKV
xxx
HSxxx
TO GC / ANALYTICAL
FQTxxx
FQIxxx
FQI-xxx
F-xxx
LITxxx
PCVxxx
LICxxx
IA
IP
LYxxx
LVxxx
FC
HYDROISOMERIZED PRODUCT
WAH
WAL
V-xxxHYDROISOMERIZED PRODUCT RECEIVER
HV-xxx
WTxxx
WIxxx
E
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
TIC
xxx
TExxx
TYxxx
TSS
xxx
TExxx
HV-xxx
HV-xxx
TI
xxx
TExxx
TI
xxx
TExxx
TI
xxx
TExxx
TI
xxx
TExxx
TI
xxx
TExxx
PTxxx
PI
xxxPIxxx
VENT
PSVxxx
Our Current Projects
At the present time, some of the projects that we are working on are strange and interesting. Some examples are:
Recirculating fluidized bed based pyrolysis of biomass to produce pyoil
Monetization of natural gas into methanol using modular construction technologies
Monetization of natural gas into DME using catalytic distillations
Conversion of triglycerides into jet fuels using catalytic decarboxylation and catalytic hydroisomerization
Pilot plant to study and optimize next generation CO2 absorbing technologies
Eight reactor hydrotreating pilot plant
Biomass oxyblown gasification for syngas production
Upgrading of tar sand derived bitumens
Why Pilot Plants?
Commit your blunders on a small scale and make your profit on a large scale.
Pilot and demo plants represent the intermediate state between laboratory studies and industrial plants.
The pilot and demo plant must be understood not as a scale-up of laboratory units but as a small scale simulation of the future industrial plant.
xxx
The objectives of a pilot plant, therefore, can differ depending on the specific circumstances of each project, and the decision for its construction can include one or several of the following objectives:
To optimize the operating parameters of the process,
To study the effects of recirculating process streams and of accumulation of impurities over long periods,
To obtain process information necessary to specify and design the full scale plant,
To test process control systems and procedures,
To test materials of construction,
To optimize the design of the equipment,
To obtain sufficient information to prepare detailed and reliable estimates of capital and operating costs and to prepare a reliable economic evaluation of the project,
To gain operating experience. and to train the personnel that will operate the full scale plant,
To identify hazards in the process and ensure safety in design and operation, including the disposal of radioactive wastes,
To produce a reasonable amount of uranium concentrate for characterization and for use in subsequent stages of the nuclear fuel cycle.
top related